JP4301375B2 - Durable and translucent laminated film material - Google Patents

Description

  The present invention relates to a laminated film material having high durability and translucency. More specifically, the present invention is excellent in water resistance, antifouling property, daylighting property (visible light transmission property), weather resistance, and therefore has high durability, such as tennis court, golf driving range, baseball field and swimming pool. The present invention relates to a laminated film material suitable for sports facilities, exhibition and event venues, and buildings such as warehouses.

  In recent years, buildings such as tennis courts, golf driving ranges, baseball fields, swimming pools, and other sports facilities, exhibition / event venues, and warehouses, in which the roof portion is made of a membrane material, are increasing. Membrane structures using these membrane materials are light in the roof and easy to sew (join), making it possible to use a large span structure and shortening the work period required for the construction of the roof. It has the feature that it is possible. Furthermore, as another purpose of using the membrane material for the roof part, an attempt is made to use the excellent daylighting property of the membrane material, for example, to save energy for lighting in the daytime or to create a comfortable environment incorporating natural light. It has been done. As such a film material, a material obtained by laminating a vinyl chloride resin layer, a silicon resin layer, a tetrafluoroethylene resin layer or the like on a fiber base fabric made of polyester fiber cloth, glass fiber cloth or the like is known. However, when these lighting properties and transparency are improved, the weather resistance deterioration due to ultraviolet rays of the fiber base fabric and the water resistance deterioration due to moisture such as moisture become prominent, and it has not been able to withstand long-term use.

  As a method for improving these defects, for example, JP-A-4-182185 (Patent Document 1) includes a method of adding an organic ultraviolet absorber to the outermost vinyl chloride resin film as a means for maintaining transparency. Are listed. However, in this method, due to long-term outdoor use, the organic ultraviolet absorber blooms or volatilizes over time, the ultraviolet shielding ability decreases, the film layer surface deteriorates, and the fiber base fabric strength decreases, In addition to transparency, there was a problem that the strength as a film material was significantly reduced.

  In addition, JP-A-7-304924 (Patent Document 2) adds a silane-coupled titanium oxide superconducting powder to a tetrafluoroethylene resin layer formed on a glass fiber base fabric to improve weather resistance. A method of providing is disclosed. However, with this method, although excellent weather resistance can be imparted, the addition of titanium oxide particles inevitably results in a decrease in translucency and transparency, and the glass fiber wear damage due to titanium oxide particles occurs. However, the strength of the fiber base fabric is reduced.

JP-A-9-25348 (Patent Document 3) discloses a film material in which a low molecular weight acrylate ultraviolet absorber having a molecular weight of 1000 or less is added to a fluororesin film stuck on a fiber base fabric. Yes. Although this method can maintain transparency, it has the disadvantage that the ultraviolet absorber will bloom over time, and the long-term outdoor use will reduce the ultraviolet absorbing ability and reduce the strength of the fiber base material. It was.
JP-A-4-182185 Japanese Patent Laid-Open No. 7-304924 Japanese Patent Laid-Open No. 9-25348

The present invention is excellent in visible light transmittance (lighting property), weather resistance, antifouling property and water resistance, and can maintain a practically sufficient mechanical strength over a long period of time. An object of the present invention is to provide a laminated film material having high light properties.
The present invention also requires daylighting, water resistance and long-term weather resistance, such as tennis courts, golf driving ranges, baseball fields, pools, other sports facilities, exhibition and event venues, and warehouses. An object of the present invention is to provide a laminated film material having high durability and high translucency useful for a building.

The laminated film material having high durability and high translucency according to the present invention includes a base fabric made of a fiber fabric, an adhesive resin layer formed on at least one surface of the base fabric, and the base through the adhesive resin layer. And at least one fluorine-containing resin outer surface layer adhered to the cloth,
The adhesive resin layer is composed of an adhesive resin lower layer formed on the base fabric, and an adhesive resin upper layer formed between the adhesive resin lower layer and the fluorine-containing resin outer surface layer,
The adhesive resin lower layer has a fluorine-containing binder resin crosslinked with a crosslinking agent containing at least one selected from an isocyanate compound and a coupling agent compound, an average molecular weight of 10,000 or more, and an average particle size of 100 nm or less. A weather resistance improver comprising a particulate high molecular weight UV absorber having
The adhesive resin upper layer includes fine particle titanium oxide having an average particle size of 100 nm or less, and a fluorine-containing binder resin crosslinked with at least one crosslinking agent selected from an isocyanate compound and a silane coupling agent compound,
As a whole, it has a visible light transmittance of 15% or more.
In the laminated film material having high durability and high translucency according to the present invention, the fiber fabric for the base fabric is selected from coarse woven fabrics in which warp yarns and weft yarns are arranged in parallel with each other with an interval between yarns. Is preferred.
In the laminated film material having high durability and high translucency according to the present invention, the particulate high molecular weight ultraviolet absorber is at least one ultraviolet absorbing monomer selected from a 2-hydroxybenzophenone compound and a 2-hydroxybenzotriazole compound. And at least one selected from a copolymer of the UV-absorbing monomer and a copolymerizable monomer.
The fluorine-containing resin used in the laminated film material having high durability and translucency according to the present invention is vinylidene fluoride, ethylene trifluoride, ethylene trifluoride chloride, ethylene tetrafluoride, propylene hexafluoride, fluoroalkyl. It is preferable to include a fluorine-containing copolymer resin containing at least one of vinyl ether and at least two copolymers selected from ethylene.
In the highly durable and translucent laminated film material of the present invention, the fluorine-containing copolymer resin for the fluorine-containing resin outer layer includes a tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride terpolymer. It is preferable.
In the laminated film material having high durability and high translucency according to the present invention, the visible light transmittance of the fluorine-containing resin outer surface layer is preferably 70% or more.
In the laminated film material having high durability and high translucency according to the present invention, the fluorine-containing resin outer surface layer preferably has a visible light transmittance of 90% or more and is substantially transparent. In the laminated film material having high durability and high translucency according to the present invention, the fluorine-containing binder resin for the adhesive resin layer preferably contains a tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride terpolymer. .

  The laminated film material of the present invention is excellent in durability and translucency, has little water deterioration and climate deterioration even in long-term outdoor use, has high antifouling properties, daylighting properties, and strength retention properties. It is useful for buildings such as commercial facilities, exhibition halls, event halls, and warehouses.

One embodiment of the laminated film material having high durability and high translucency according to the present invention is shown in FIG.
In the laminated film material of FIG. 1, an adhesive resin lower layer 2 is formed and bonded on one side of a base fabric 1 made of a fiber fabric, an adhesive resin upper layer 4 is formed and bonded thereon, and further, A fluorine-containing resin outer surface layer 3 is formed and bonded.

  Base fabrics used in the laminated film material of the present invention are natural fibers such as cotton and hemp, inorganic fibers such as glass fibers, regenerated fibers such as viscose rayon and cupra, semisynthetic fibers such as di- and Triacetate fibers and the like, and synthetic fibers such as nylon 6, nylon 66, polyester (polyethylene terephthalate, etc.) fibers, aromatic polyamide fibers, acrylic fibers, polyolefin fibers and the like may be selected. it can. Among these fabrics, a polyester fiber fabric is preferably used when high flexibility is required, and a glass fiber fabric is preferably used when high film material strength and durability are required.

  The fibers in the fabric may have any shape such as short fiber spun yarn, long fiber yarn, split yarn, tape yarn or the like. The base fabric structure may be a woven fabric, a knitted fabric, a non-woven fabric, or a composite thereof, but at least a coarse texture composed of yarns including warps and wefts arranged in parallel with a gap between yarns. The knitted woven fabric is preferably a non-coarse knitted woven fabric, and in particular, the knitted woven fabric is preferably a coarse knitted woven fabric from the viewpoint of daylighting, transparency and transparency. As the woven structure of the coarse knitted fabric, a mesh-shaped woven structure having a visible light transmittance of 20 to 95%, for example, a plain weave, a basket weave, or a dummy weave is preferable. When the visible light transmittance of the base fabric is less than 20%, when a fluorine-containing resin layer is laminated thereon, the obtained laminated film material cannot exhibit effective translucency, and the visible light transmittance is low. If it exceeds 95%, the resulting base fabric cannot maintain the strength of the membrane material to a practical level. The woven structure of the base fabric can be appropriately selected according to the purpose, use, and desired visible light transmittance of the laminated film material,

  As such a woven structure, when the desired visible light transmittance of the laminated film material of the present invention is 15 to 35%, for example, glass filament yarn of 202.5 Tex is used, and the yarn density of warp and weft is 15 to 20 It is preferable to set this to 25.4 mm. Further, when using, for example, a 750D filament yarn as the polyester fiber, the yarn density of the warp and the weft is preferably 15 to 20 / 25.4 mm. Further, when the desired visible light transmittance of the laminated film material of the present invention is 35% or more, for example, when a glass filament yarn of 202.5 Tex is used, the yarn density of warp and weft is 3 to 15 / 25.4 mm. preferable. For example, when a polyester filament yarn of 750D is used, the yarn density of the warp and weft is preferably 5 to 15 / 25.4 mm.

  The fluorine-containing resin used in the laminated film material of the present invention is selected from the group consisting of vinylidene fluoride, ethylene trifluoride, ethylene trifluoride chloride, ethylene tetrafluoride, hexafluoropropylene, fluoroalkyl vinyl ether, and ethylene. A copolymer resin composed of two or more kinds of monomers can be preferably used. In particular, it is preferable to use a terpolymer resin of tetrafluoroethylene, hexafluoropropylene, and vinylidene fluoride from the viewpoints of transparency, flexibility, high-frequency sewing properties, and workability. Examples of the tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride terpolymer resin include “THV200G”, “THV400G”, and “THV500G” manufactured by Sumitomo 3M Limited. In addition, in the fluorine-containing resin, an antioxidant, an ultraviolet absorber, a filler, a lubricant, a colorant, and the like can be appropriately added depending on the purpose and use of the laminated film material. The visible light transmittance of the fluororesin layer after adding is preferably 70% or more. Furthermore, it is desirable from the viewpoint of transparency and daylighting to use a substantially transparent film having a visible light transmittance of 90% or more.

  In the laminated film material of the present invention, an adhesive resin layer is provided between the base fabric and the fluorine-containing resin outer surface layer. The adhesive resin layer is formed for the purpose of adhering the base fabric and the fluorine-containing resin outer surface layer, but further, water absorption phenomenon to the fiber bundle included in the base fabric, volatilization of the UV absorber, deterioration of water resistance due to migration. This is effective for preventing the light-transmitting deterioration due to the ultraviolet rays of the base fabric itself, and preventing the deterioration of the light-transmitting property due to the adhesive resin layer. The adhesive resin layer is composed of an adhesive resin lower layer formed on the base fabric, and an adhesive resin upper layer formed between the adhesive resin lower layer and the fluorine-containing resin outer surface layer.

The fine particle high molecular weight ultraviolet absorber contained in the adhesive resin layer of the present invention includes a 2-hydroxybenzophenone structure and / or a 2-hydroxybenzotriazole structure as an ultraviolet absorbing skeleton, and the ultraviolet absorbing property described above. A copolymer of a compound having a structure and a monomer copolymerizable therewith is used.
Examples of the 2-benzophenone compound serving as an ultraviolet absorption skeleton include 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methacryloyloxyethoxybenzophenone, 2-hydroxy-4- (2-acryloyloxy) ethoxybenzophenone, and the like. The 2-benzotriazole compound is preferably 2- [2′-hydroxy-5 ′-(acryloyloxy) phenyl] benzotriazole or 2- [2′-hydroxy-5 ′-(methacryloyloxy) phenyl. Benzotriazole, 2- [2'-hydroxy-5 '-(methacryloyloxyethyl) phenyl] benzotriazole, 2- [2'-hydroxy-5'-(acryloyloxyethyl) phenyl] benzotriazole, 2- [ 2 ' Hydroxy-5 '- (methacryloyloxy propyl) phenyl] -5-chloro-benzotriazole, and 2- [2'-hydroxy-5' - be used as the (meth acryloxymethyl oxymethyl) phenyl] benzotriazole it preferred.

  Monomers that can be copolymerized with the compound having the UV-absorbing structure include acrylic acid, methacrylic acid and alkyl esters thereof such as acrylic acid, methacrylic acid, methyl acrylate, methyl methacrylate, butyl acrylate, and methacrylic acid. Examples include butyl, vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, acrylonitrile, and styrene, and at least one of them can be used.

  The proportion of the UV-absorbing skeleton compound component in the UV-absorber copolymer is preferably 30 to 70% by weight. If this polymerization ratio is less than 30% by weight, the resulting copolymer may have insufficient ultraviolet absorbing ability, and deterioration of the fiber base fabric may not be prevented. On the other hand, if the polymerization ratio exceeds 70% by weight, the compatibility between the resulting copolymer and the fluorine-containing resin becomes insufficient, and the bleed phenomenon of the copolymer may become prominent. In addition, the molecular weight of the high molecular weight ultraviolet absorbent copolymer needs to be 10,000 or more in order to prevent volatilization of the ultraviolet absorbent and the bleed phenomenon over time. If it is less than 10,000, the bleed phenomenon becomes remarkable, and the weather resistance and water resistance of the fiber base fabric become insufficient. In addition, as the molecular weight of the ultraviolet absorber copolymer is increased, the average particle size of the particles increases. However, in order to prevent a decrease in visible light transmittance, the average particle size may be 100 nm or less. is necessary. When the average particle size is larger than 100 nm, the visible light transmittance is lowered due to light scattering.

  As the high molecular weight ultraviolet absorber copolymer satisfying such requirements, divinylbenzene, trivinyl chloride, and / or 2-hydroxybenzophenone compound and / or 2-hydroxybenzotriazole compound and a copolymerizable monomer are subjected to a polymerization reaction. A crosslinkable monomer having two or more double bonds in the molecule, such as allyl methacrylate, or a crosslinkable monomer having a self-condensable functional group, such as glycidyl methacrylate, methacrylamide, etc. It is preferable to use an aqueous emulsion type ultraviolet absorber obtained by emulsion polymerization of the polymer in order to obtain ultraviolet absorber particles having a high molecular weight and an average particle size of 100 nm or less, and having high dispersibility in an aqueous binder resin. Is also preferable. As such a high molecular weight ultraviolet absorber, for example, “ULS-383MG” (manufactured by Yushi Kogyo Co., Ltd.) can be used.

  The addition amount of the polymeric ultraviolet absorber is preferably 1 to 30% by weight with respect to the total solid weight of the adhesive resin layer. When the addition amount is less than 1% by weight, the ultraviolet shielding ability may be insufficient. When the addition amount exceeds 30% by weight, the adhesion of the resulting adhesive resin layer to the fiber base fabric becomes insufficient, and the light transmittance There is a case where the decrease in the resistance becomes significant.

  The fine particle titanium oxide may be obtained by any of the chlorine method and the sulfuric acid method, and the crystal structure may be either a rutile type or an anatase type. The average particle diameter needs to be 100 nm or less from the viewpoint of visible light transmittance, and is preferably 50 nm or less. When the average particle diameter exceeds 100 nm, the transmissivity of the resulting adhesive resin layer becomes insufficient, and particularly when glass fiber is used for the base fabric, damage to the glass fiber by titanium oxide is promoted, The durability of the cloth strength decreases. In particular, when used in combination with a high molecular weight ultraviolet absorber, the ultraviolet shielding ability can be further improved without impairing the adhesion between the resulting adhesive resin layer and the fiber base fabric.

  The addition amount of the fine particle titanium oxide is preferably 0.1 to 15% by weight with respect to the total solid weight of the adhesive resin upper layer. If it is less than 0.1% by weight, the UV shielding ability may be insufficient, and if it exceeds 15% by weight, the visible light transmittance of the resulting adhesive resin layer will be insufficient. When using a fiber for a base fabric, the strength of the glass fiber itself may be lowered.

The adhesive resin layer of the present invention has at least one selected from an isocyanate compound and a coupling agent as a cross-linking agent for a fluorine-containing binder resin in order to improve adhesion to a fiber base fabric and improve water resistance. These compounds are used.
The coupling agent used in the present invention includes at least one selected from silane coupling agents, titanium coupling agents, zirconium coupling agents, aluminum coupling agents, and zircoaluminum coupling agents. It is preferable to use it.

  Examples of the silane coupling agent include aminosilanes such as γ-aminopropyltriethoxysilane and N-phenyl-γ-aminopropyltriethoxysilane; epoxy silanes such as γ-glycidoxypropylmethyldiethoxy. Silane, γ-glycidoxypropyltrimethoxysilane, and β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane; vinyl silanes such as vinyltriethoxysilane and vinyltris (β-methoxyethoxy) silane; mercaptosilane Such as γ-mercaptopropyltrimethoxysilane.

  Examples of titanium coupling agents include alkoxy titaniums such as tetraisopropoxy titanium, tetra-n-butoxy titanium and tetrakis (2-ethylhexoxy) titanium; titanium acylates such as tri-n-butoxy titanium stearate. And isopropoxy titanium tristearate.

Examples of the zirconium coupling agent include tetrabutyl zirconate, tetra (triethanolamine) zirconate, and tetraisopropyl zirconate.
Examples of the aluminum coupling agent include acetoalkoxyaluminum diisopropylate.
Furthermore, examples of the zircoaluminum-based coupling agent include tetrapropylzircoaluminate.

  Among these coupling agents, from the viewpoints of water resistance and weather resistance, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropyltrimethoxysilane, and β- (3,4 epoxycyclohexyl) ethyl are particularly preferred. It is preferable to use an epoxy silane such as trimethoxysilane.

  Isocyanate compounds used as crosslinking agents for fluorine-containing binder resins include aliphatic diisocyanates such as hexamethylene diisocyanate and lysine diisocyanate; alicyclic diisocyanates such as isophorone diisocyanate and hydrogenated tolylene diisocyanate; At least selected from group diisocyanates such as tolylene diisocyanate, diphenylmethane diisocyanate and xylene diisocyanate; isocyanurates such as tris (hexamethylene isocyanate) isocyanurate and tris (3-isocyanatomethylbenzyl) isocyanurate One or the end of the isocyanate group of these compounds is phenols, oximes, alcohols It is preferable to use a modified isocyanate hydrophilic monomer is added as and a portion of the isocyanate groups of the compounds, such as ethylene glycol; blocked isocyanates blocked with a blocking agent selected from such lactams. From the viewpoint of dispersibility, water resistance, and adhesion to a base fabric, when used in an emulsion resin solution, in particular, one of the isocyanate groups of blocked isocyanate and aliphatic isocyanate has a hydrophilic unit such as ethylene glycol. It is preferable to use a modified partially trimerized isocyanurate to which a monomer is added.

  It is preferable that the addition amount of a coupling agent and isocyanate is 0.5-30 weight% with respect to the total solid content weight of an adhesive resin layer. If the amount added is less than 0.5%, the adhesion between the resulting adhesive resin layer and the fiber base fabric and its water resistance may be insufficient, and if it exceeds 30% by weight, the resulting laminate The flexibility of the film material may be insufficient.

  As the binder resin contained in the adhesive resin layer of the present invention, a fluorine-containing resin is used. This is excellent in adhesiveness with the fluorine-containing resin outer surface layer, and is suitable in terms of water resistance and weather resistance. For example, tetrafluoroethylene, hexafluoropropylene, vinylidene fluoride, trifluoroethylene chloride, ethylene-tetrafluoro A solution dispersion type or a water dispersion type of a polymer of one kind of monomer selected from ethylene or fluoroalkyl vinyl ether, or a copolymer of two or more kinds of monomers can be preferably used. In particular, it is preferable to use an aqueous dispersion of a tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride terpolymer resin from the viewpoint of flexibility, high-frequency sewing properties, and durability. As such a resin, for example, a dispersion type “THV350C” manufactured by Sumitomo 3M Limited can be used.

  If necessary, one or more of an acrylic resin and a polyurethane resin may be used in combination with the fluorine-containing binder resin. In the present invention, the adhesive resin layer is composed of two upper and lower layers. Since the glass fiber is used as the base fabric in the composite film body of the present invention, the first resin layer is high for the purpose of avoiding fiber damage due to titanium oxide. An adhesive resin lower layer composed of a molecular weight ultraviolet absorber, at least one compound selected from an isocyanate compound and a coupling agent, and a binder resin is provided, and further, a fine particle titanium oxide, an isocyanate compound and a coupling agent are selected thereon. By providing an adhesive upper layer made of at least one kind of compound and binder resin, the durability of the obtained laminated film material can be improved.

The laminated film material of the present invention has a fiber base fabric and a fluorine-containing resin outer surface layer laminated on at least one side thereof, and an adhesive resin upper / lower layer is formed between the fiber base fabric and the fluorine-containing resin outer surface layer. Laminated body.
As its production method, the adhesive resin layer can be formed by a method such as gravure roll coating, doctor blade coating, reverse roll coating, dip coating or the like. The fluorine-containing resin outer surface layer is formed by laminating a fluorine-containing resin film formed by a method such as a calender molding method or an extrusion molding method using a T-die on the adhesive resin layer by a method such as thermocompression bonding.
The visible light transmittance of the laminated film material produced by the above method is 15% or more, preferably 20% or more, from the viewpoint of the daylighting and heating efficiency inside the building constituted by this film material. .

  The present invention will be described more specifically with reference to the following examples. The measurement methods used for performance evaluation of products in each example are as follows.

(1) Visible light transmittance The total light transmittance was measured based on JIS K-7105.
(2) Weather resistance A metal weather super accelerated weathering tester (manufactured by Dainippon Plastic Co., Ltd.) was used to measure and evaluate the retention of tensile strength and adhesive strength after ultraviolet irradiation under the following test conditions.
UV intensity: 50 (mW / cm ² )
L time (light); temperature 60 ° C, humidity 39%, set time 4 hours D time (condensation); temperature 60 ° C, humidity 90% or more, set time 4 hours Total time at L time and D 8 hours 1 cycle As a result, a total of 15 cycles (120 hours) was set as one unit of test time, and irradiation was performed for a total of 10 units of 1200 hours.

(3) Water resistance test The tensile strength and adhesive strength retention after immersion in warm water at 40 ° C for 1 week were evaluated.
(4) Flexibility test Tensile strength retention was evaluated according to JIS K-5400.

Reference example 1
Fabric using glass fiber yarn (fiber thickness: DE yarn, woven yarn thickness: 337.5Tex / 2) as warp and weft as a base fabric (mummy weave, basis weight: 270 g / m ²⁾ , density: warp 4 / 25.4 mm, 5 weft / 25.4 mm). The visible light transmittance of this base fabric was 70%. This base fabric was dipped in a resin liquid for forming an adhesive resin underlayer having the following composition, drawn, dried and solidified to form an adhesive resin lower layer on the surface of the base fabric. Further thereon, an adhesive resin upper layer forming solution was formed using an adhesive resin upper layer forming dissolved resin solution having the following composition.
(Resin liquid composition for adhesive resin underlayer)
100 parts by weight of vinylidene fluoride-4 ethylene fluoride-6 propylene (manufactured by Sumitomo 3M Limited; trademark: THV-350C, dispersion, solid content 50%)
40 parts by weight of an emulsion type high molecular weight ultraviolet absorber (manufactured by Yushi Kogyo Co., Ltd .; trademark: ULS-383MG, molecular weight of 1 million or more, average particle size 70 nm, solid content 30%)
Silane coupling agent 3 parts by weight (β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane)
The solid content by weight of the components of the resin liquid is 76.9% by weight of the resin binder, 18.5% by weight of the high molecular weight ultraviolet absorber, 4.6% by weight of the coupling agent, and the coating amount is 125 g. / M ² . Moreover, the visible light transmittance after forming the adhesive resin layer was 62%.

  Tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride terpolymer resin (manufactured by Sumitomo 3M Co., Ltd .; trademark: THV-400G) is used as the fluorine-containing resin used for the outer surface layer of the fluorine-containing resin. 0.5 parts by weight of an amide lubricant was blended as an auxiliary agent, and the resulting resin composition was kneaded and rolled by a calendering method to produce a 0.20 mm thick film. The visible light transmittance of this film was 85%. This film is thermocompression bonded to the adhesive resin layers formed on both sides of the fiber base fabric at 170 ° C. for 2 minutes, respectively, to crosslink the adhesive resin layer, and through this, the fluorine-containing resin film is used as the base fabric. Glued. A laminated film material of the present invention was obtained. The composition and test results of this film material are shown in Table 1 and Table 3, respectively.

Reference example 2
A laminated film material was produced and tested in the same manner as in Reference Example 1. However, 5 parts by weight of fine particle titanium oxide (STT-4 manufactured by Titanium Industry Co., Ltd.) having an average particle size of 30 nm was further added to the composition of the adhesive resin lower layer. At this time, the amount of blended solid components was 71.4% by weight for the resin binder, 17.1% by weight for the high molecular weight ultraviolet absorber, 7.1% by weight for the fine particle titanium oxide, and 4.3% by weight for the coupling agent. there were. The composition and test results of this film material are shown in Table 1 and Table 3, respectively.

Example 1
A laminated film material was produced and tested in the same manner as in Reference Example 1. However, an adhesive resin lower layer was formed from a resin liquid having the following composition, and an adhesive resin upper layer was further formed thereon from an additional resin liquid having the following composition.
(Resin solution for adhesive resin underlayer)
Vinylidene fluoride-4 ethylene fluoride-6 propylene 100 parts by weight (manufactured by Sumitomo 3M; THV-350C, dispersion, solid content 50%)
Emulsion type high molecular weight ultraviolet absorber 40 parts by weight (manufactured by Yushi Kogyo Co., Ltd .; ULS-383MG, molecular weight 1 million or more, average particle size 70 nm, solid content 30%)
3 parts by weight of coupling agent (β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane)

(Resin liquid for adhesive resin upper layer)
Vinylidene fluoride-4 ethylene fluoride-6 propylene 100 parts by weight (manufactured by Sumitomo 3M; THV-350C, dispersion, solid content 50%)
Particulate titanium oxide 5 parts by weight (Ishihara Sangyo Co., Ltd .; TTO-55, primary particle size 35 nm)
3 parts by weight of coupling agent (β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane)

At this time, the blended solid component amounts were 76.9% by weight of the resin binder, 18.5% by weight of the polymer ultraviolet absorber, and 4.6% by weight of the coupling agent in the adhesive resin lower layer. Was 80 g / m ² . In the upper layer of the adhesive resin, the resin binder was 86.2% by weight, the fine particle titanium oxide was 8.6% by weight, the coupling agent was 5.2% by weight, and the coating amount was 30 g / m ² . Table 1 and Table 3 show the composition and test results of this laminated film material, respectively.

Comparative Example 1
A film material was produced and tested in the same manner as in Reference Example 2. However, without providing an adhesive resin lower layer, a fluorine-containing resin film was directly laminated on both surfaces of the fibrous base fabric to form an outer surface layer. Tables 2 and 3 show the composition and test results of this film material, respectively.

Comparative Example 2
A film material was produced and tested in the same manner as in Reference Example 2. However, the polymer ultraviolet absorber in the lower layer of the adhesive resin was changed to a low molecular weight ultraviolet absorber (manufactured by Johoku Chemical Co., Ltd .; molecular weight 225.3, average particle size of 10 nm or less). Tables 2 and 3 show the composition and test results of this film material, respectively.

Comparative Example 3
A film material was produced and tested in the same manner as in Reference Example 2. However, a high molecular weight ultraviolet absorber having a large particle size as a polymeric ultraviolet absorber for the lower layer of the adhesive resin (on the other hand, manufactured by Yushi Kogyo Co., Ltd .; ULS-383MG; Was used. Tables 2 and 3 show the composition and test results of this film material, respectively.

Comparative Example 4
A film material was produced and tested in the same manner as in Reference Example 2. However, titanium oxide having a primary particle diameter of 300 nm was used as fine particle titanium oxide in the lower layer of the adhesive resin. Tables 2 and 3 show the composition and test results of this film material, respectively.

Comparative Example 5
A film material was produced and tested in the same manner as in Reference Example 2. However, 5 parts by weight of titanium oxide having an average particle diameter of 300 nm was contained in the fluorine-containing resin outer layer film. The film obtained had a light transmittance of 45%. This film was directly laminated on both sides of the fiber base fabric without using an adhesive resin layer. Tables 2 and 3 show the composition and test results of this film material, respectively.

  The laminated film material having high durability and translucency according to the present invention has little water deterioration and climate deterioration even in long-term outdoor use, and is excellent in antifouling properties, daylighting properties, and strength retention properties. It is useful for sports facilities such as golf driving ranges, baseball fields, and pools, exhibition halls, event halls, and warehouses.

Cross-sectional explanatory drawing which shows the laminated structure of an example of the highly durable laminated film material of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Base fabric 2 Adhesive resin lower layer 3 Fluorine-containing resin outer surface layer 4 Adhesive resin upper layer

Claims (8)

A base fabric made of glass fiber fabric, an adhesive resin layer formed on at least one surface of the base fabric, and at least one fluorine-containing resin outer surface layer bonded to the base fabric via the adhesive resin layer Including
The adhesive resin layer is composed of an adhesive resin lower layer formed on the base fabric, an adhesive resin upper layer formed between the adhesive resin lower layer and the fluorine-containing resin outer surface layer,
The adhesive resin lower layer has a fluorine-containing binder resin crosslinked with a crosslinking agent containing at least one selected from an isocyanate compound and a coupling agent compound, an average molecular weight of 10,000 or more, and an average particle size of 100 nm or less. A weather resistance improver comprising a particulate high molecular weight UV absorber having
The adhesive resin upper layer includes fine particle titanium oxide having an average particle size of 100 nm or less, and a fluorine-containing binder resin crosslinked with at least one crosslinking agent selected from an isocyanate compound and a silane coupling agent compound,
A laminated film material having high durability and high translucency, characterized by having a visible light transmittance of 15% or more as a whole.   2. The durable and translucent laminated film according to claim 1, wherein the fiber fabric for base fabric is selected from coarse woven fabrics in which warp yarns and weft yarns are arranged in parallel to each other with an interval between yarns therebetween. Wood.   The particulate high molecular weight ultraviolet absorber is a copolymer of at least one ultraviolet absorbing monomer selected from 2-hydroxybenzophenone compounds and 2-hydroxybenzotriazole compounds and a monomer copolymerizable with the ultraviolet absorbing monomer. The laminated film material having high durability and high translucency according to claim 1, comprising at least one selected from polymers.   The fluorine-containing resin is at least one of at least two copolymers selected from vinylidene fluoride, ethylene trifluoride, ethylene trifluoride chloride, ethylene tetrafluoride, propylene hexafluoride, fluoroalkyl vinyl ether, and ethylene. The laminated film material having high durability and high translucency according to claim 1, comprising a fluorine-containing copolymer resin containing one kind.   The laminate having high durability and translucency according to claim 4, wherein the fluorine-containing copolymer resin for the fluorine-containing resin outer surface layer is a terpolymer of ethylene tetrafluoride-propylene hexafluoride-vinylidene fluoride. Membrane material.   The laminated film material having high durability and high translucency according to any one of claims 1, 4, and 5, wherein the visible light transmittance of the fluorine-containing resin outer surface layer is 70% or more.   The durability and translucency according to any one of claims 1 and 4 to 6, wherein the fluorine-containing resin outer surface layer has a visible light transmittance of 90% or more and is substantially transparent. Laminated film material.   The laminated film material having high durability and high translucency according to claim 1, wherein the fluorine-containing binder resin for the adhesive resin layer is a tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride terpolymer.

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